Anti-reflective coating for photovoltaic glass panel

ABSTRACT

A method of making an anti-reflective film comprises preparing a liquid composition with specific amounts of tetraethyl orthosilicate, polyethylene glycol, HCl, ethanol and at least one alcohol having a higher boiling point than ethanol and miscibility with both ethanol and water; applying the liquid composition onto a surface of a substrate to form a liquid film; evaporating the ethanol and the at least one alcohol from the liquid film to form a solid film; and heating the solid film to form a silica film.

This application claims benefit of U.S. Provisional Application No.60/894,001, filed Mar. 9, 2007, which is hereby incorporated byreference in its entirety into the present application.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to an anti-reflective coating. Inparticular, the present invention relates to an anti-reflective coatingthat can be used to increase the light transmission of glass used in themanufacture of solar modules, and to a method of making theanti-reflective coating.

2. Discussion of the Background

All United States patents and application Publications referred toherein are incorporated by reference in their entireties. In the case ofconflict, the present specification, including definitions, willcontrol.

Solar modules have been developed that convert light into electricity.These modules typically include an outer layer of glass. The differencein the index of refraction between the glass and air can lead to anundesirable partial reflection of light from the glass that reduces theamount of incident light that can be converted into electricity by themodule.

Some success at reducing the reflection has been achieved by forming lowindex of refraction coatings of silica on the glass. U.S. Pat. No.7,128,944 discloses low index silica coatings formed by coating theglass with an aqueous coating solution and a surfactant mixture, theaqueous coating solution having a pH of 3 to 8, containing 0.5 wt. % to5.0 wt. % [SiO_(x)(OH)_(y)]_(n) having a particle size of 10 nm to 60nm, and a surfactant mixture; drying the coated glass; thermaltoughening at temperatures of at least 600° C.; and thermal tempering ofthe coated glass by a forced air flow.

Other low index silica coatings have been formed by dipping a glasssubstrate in a mixture of tetraethyl orthosilicate and ethanol to form aliquid film on the glass, or by spraying on the glass a mixture oftetraethyl orthosilicate and ethanol to form a liquid film; evaporatingthe ethanol from the liquid film to form a film residue; and thenheating the film residue to convert the tetraethyl orthosilicate intosilica. Including polyethylene glycol in the liquid films has been foundto create pores in the silica films during the heating that furtherlower the index of refraction of the silica and increases lighttransmission.

However, silica coatings formed using liquid films containing tetraethylorthosilicate, polyethylene glycol and ethanol have not shown aconsistent improvement in transmission. Accordingly, there is a need inthe art for anti-reflection films that achieve improved properties withconsistency and methods of preparing such films.

SUMMARY OF THE INVENTION

The present invention provides a method of making an anti-reflectivefilm that can achieve anti-reflective properties with greaterconsistency than those currently known in the art. In particular, thepresent invention provides methods that allow for fast and consistentproduction of coatings that increase the light transmission through asubstrate. For purposes herein, light transmission is taken to mean theratio of the amount of photons passing thru a given substrate to theamount of photons incident upon the given substrate. Furthermore, thepresent invention provides a method for making a coating that improves“anti-reflective coating efficiency”. For purposes herein,anti-reflective coating efficiency is taken to mean the increase inlight transmission provided by a coating film on a given substratecompared to an uncoated given substrate.

Accordingly, the invention provides a method of preparing a coatingcomprising Si on a substrate comprising: (i) preparing a compositioncomprising a compound comprising Si and O, a polymeric glycol, a strongacid, at least a first alcohol, at least a second alcohol and water;(ii) applying the composition onto a surface of a substrate to form afilm; (iii) evaporating the alcohols from the film; and (iv) heating thefilm.

Methods in accordance with the present invention utilize a series ofchemical moieties which, when applied to at least one surface of asubstrate and heated, provide the inventive features described herein.The chemical moieties are preferably compounds that comprise both Si andO, polymeric glycols, strong acids and alcohols. Aqueous solutions ofthese compounds, when applied to at least one surface of a substrate,allow for the production of a thin film coating that increases the lighttransmission through a substrate as well as the anti-reflective coatingefficiency.

One aspect of the present invention is found to be driven by the ratioof polymeric glycol to a compound comprising Si and O. Another aspect ofthe present invention is found to be driven by the evaporation rates ofthe solvents from the starting composition. When the solvent comprisesmore than one alcohol, the evaporation rate of the alcohols may becontrolled in such a way as to improve the application process.

It has been found that when the solvent comprises more than one alcohol,wherein one alcohol has a higher boiling point than the other, areduction in undesirable evaporation of the solvent during applicationto at least one surface of a substrate is observed. Such undesirableevaporation can increase costs for both materials and cleanup and canalso produce uneven liquid films that do not adequately wet thesubstrate. Having more than one alcohol present in the startingcomposition enhances the anti-reflective coating efficiency.

BRIEF DESCRIPTION OF THE DRAWINGS

The preferred embodiments of the invention will be described in detail,with reference to the following figures, where:

FIG. 1 shows a glass substrate;

FIG. 2 shows a liquid film on a glass substrate

FIG. 3 shows a solid film on a glass substrate; and

FIG. 4 shows a silica film on a glass substrate.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

The invention provides a method of preparing a porous silica coating ona substrate comprising: (i) preparing a composition comprising acompound comprising Si and O, a polymeric glycol, a strong acid, atleast a first alcohol, at least a second alcohol and water; (ii)applying the composition onto a surface of a substrate to form a film;(iii) evaporating the alcohols from the film; and (iv) heating the film.

By choosing the proper ratio of the compounds of the startingcomposition, it is possible to create on at least a surface of a glasssubstrate, a coating with a lower refractive index than the glass. Forpurposes herein, the refractive index is a measure for how much thespeed of light is reduced inside a given substrate as compared to air.

The present invention provides a method of making an anti-reflectivefilm, the method may comprise preparing a liquid composition comprising0.1 to 15 volume % of a compound comprising Si and O, 0.1 to 80 g(preferably 0.1 to 25 g, more preferably 0.1 to 20.0 g) of a polymericglycol per liter of the liquid composition, 0.1 to 20.0 g of a strongacid per liter of the liquid composition, 0.1 to 80 volume % (preferably0.1 to 30 volume %, or 0.1 to 20 volume %, or 0.1 to 15 volume %) of atleast one alcohol having a higher boiling point than at least one otheralcohol contained in the starting composition, and a balance of the atleast one other alcohol; applying the liquid starting composition onto asurface of a substrate to form a liquid film; evaporating at least thealcohols from the liquid film to form a solid film; and heating thesolid film to convert the compound comprising Si and O into a silicafilm.

An embodiment of the method of the present invention is illustrated inFIGS. 1-4. FIG. 1 shows a glass substrate 10. FIG. 2 shows applied tothe glass substrate 10 a liquid film 20 containing a compound comprisingSi and O, a polymeric glycol, a strong acid and at least two alcohols.FIG. 3 shows on the glass substrate 10 a solid film 30 formed byevaporating from the liquid film 20 the at least two alcohols. FIG. 4shows on the glass substrate 10 a silica film 40 formed by heating thesolid film 30.

The following non-limiting list of compounds are representative of themoieties that may be used in carrying out the methods of the presentinvention. Compounds comprising Si and O may be silicates, silanols,siloxanes or silanes. Preferred compounds comprising Si and O aresilicates. Most preferred compounds comprising Si and O arealkyl-orthosilicates, such as tetraethyl orthosilicate. Polymericglycols may be of the polyalkyl, polyalkene or polyalkylene type.Preferred polymeric glycols are polyethylene, polypropylene andpolybutylene glycols. The most preferred polymeric glycol ispolyethylene glycol. Alcohols may be monohydric and polyols may bedihydric, trihydric, or polyhydric. Preferred alcohols are those ofC₁-C₈ alkyl type, e.g, n-ethanol, n-propanol, n-butanol and n-pentanol.A most preferred alcohol is ethanol. Strong acids may be nitric acid,sulfuric acid, hydrochloric acid and hydrobromic acid. Preferred strongacids are hydrochloric and nitric acids.

The liquid composition is applied onto at least one surface of asubstrate that is preferably transparent to visible light. The substratecan have one or two smooth surfaces. The surface can also have one ortwo patterned surfaces. The substrate is preferable a plastic or aceramic, such as glass. More preferably, the substrate is glass. Mostpreferable, the substrate is a photovoltaic glass panel. The liquidcomposition may be applied to the surface of the substrate by spraying,dipping, brushing, spinning, or any other coating application methodknown to those of skill in the art. Preferably, the liquid compositionis sprayed, brushed or spun onto the substrate. Most preferably, theliquid composition is sprayed.

In embodiments, when the liquid composition is applied onto thesubstrate, the liquid composition and the substrate may be at roomtemperature and the substrate is at atmospheric pressure. Inembodiments, when the liquid composition to applied onto the substrate,the liquid composition and the substrate are at a temperature of 50° C.or above.

The liquid composition applied to the surface of the substrate forms aliquid film. The solvents, i.e., alcohols, evaporate, leaving a solidfilm comprising a compound comprising Si and O, a polymeric glycol and astrong acid. When the solid film is heated, the strong acid catalyzesthe conversion of the compound comprising Si and O into silica, SiO₂.Preferably, the solid film is heated to a temperature in a range of from500 to 800° C., more preferably from 650° C. to 750° C., for a period oftime in a range of from 0.5 to 5 minutes, preferably 1 to 3 minutes.During the heating step, the polymeric glycol is pyrolized, or burnedaway, leaving a porous silica film. Increasing the porosity of thesilica reduces the index of refraction of the silica, leading toimproved light transmission through a substrate.

The composition of the method of the present invention may also comprisean alcohol having a higher boiling point than the alcohol already in thestarting composition. Preferably, the alcohol having a higher boilingpoint than the already included alcohol is monohydric. More preferably,the alcohol having a higher boiling point may be propanol, butanol orpentanol. Furthermore, the alcohol having a higher boiling point musthave miscibility with both the other alcohol and water.

In preferred embodiments, the liquid composition can be prepared bymixing together 0.1 to 10 volume % of a compound comprising Si and O,0.1 to 15.0 g of a polymeric glycol per liter of the liquid composition,0.1 to 10.0 g of a strong acid per liter of the liquid composition, 0.1to 25 volume % of at least one alcohol having a higher boiling pointthan at least one other alcohol contained in the starting composition,and a balance of the at least one other alcohol.

In other preferred embodiments, the liquid composition may comprise 0.1to 10 volume % (e.g., 0.1 to 5 volume %) of a compound comprising Si andO, preferably tetraethyl orthosliicate, 0.1 to 20 volume % (e.g., 0.1 to5 volume %) of a solution of 30 g polymeric glycol, preferablypolyethylene glycol, in 100 ml water, 0.1 to 2 volume % of a solution of37 weight % strong acid, preferably hydrochloric acid, in water, 0.1 to80 volume % (e.g., 0.1 to 20 volume %) of at least one alcohol,preferably n-butanol, having a higher boiling point than at least oneother alcohol, contained in the starting composition, and a balance ofat least one other alcohol, preferably ethanol. The polymeric glycol canhave a weight average molecular weight (Mw) in a range of from 4000 to16000, with a preferable molecular weight of 6000 to 12000.

During the mixing, the ratio of the volume % of the solution ofpolymeric glycol in 100 ml water to the volume % of the solutioncontaining a compound comprising Si and O can be in a range of from 0.02to 50. To improve the anti-reflective coating efficiency, the ratio ofthe volume % of the solution of polymeric glycol in 100 ml water to thevolume % of the solution containing a compound comprising Si and O canbe at least 0.5, preferably at least 1; more preferably at least 2.

The alcohol having a higher boiling point than at least the otheralcohol and miscibility with water can have one or more hydroxyl groups.Thus, the alcohol having a higher boiling point can be monohydric,dihydric, trihydric, or polyhydric. Preferably, when the first alcoholis ethanol, the alcohol having a higher boiling point is monohydric. Inembodiments, the alcohol having a higher boiling point than ethanol canbe propanol, butanol or pentanol. Preferably, the alcohol having ahigher boiling point than ethanol is butanol, most preferably,n-butanol.

The alcohol having a higher boiling point than ethanol reducesundesirable evaporation of solvents from droplets during application,which can increase costs for both materials and cleanup and which canproduce uneven liquid films that do not adequately wet the substrate.The alcohol having a higher boiling point also reduces the evaporationrate of the liquid film, which enhances anti-reflective coatingefficiency.

Evaporation of the alcohols from the composition applied to a substratecan take 60 seconds or more.

The liquid composition is applied onto at least one surface of asubstrate. Preferably, the substrate is transparent to visible light.The substrate can be plastic or a ceramic such as glass. Preferably, thesubstrate is glass. Most preferable, the substrate is a photovoltaicglass panel. The substrate can have one or two smooth surfaces. Thesurface can also have one or two patterned surfaces.

The liquid composition can be applied to the surface of the substrate byspraying, dipping, brushing, spinning or any other coating method knownto those of skill in the art. Preferably, the liquid composition issprayed, brushed or spun onto the substrate. Most preferable, the liquidcomposition is sprayed onto the substrate.

In embodiments, when the liquid composition to applied onto thesubstrate, the liquid composition and the substrate are at roomtemperature and the substrate is at atmospheric pressure. In otherembodiments, when the liquid composition to applied onto the substrate,the liquid composition and the substrate are at a temperature of 50° C.or above.

When the solid film is heated, the strong acid catalyzes the conversionof a compound comprising Si and O into silica, SiO₂. Preferably, thesolid film is heated to a temperature in a range of from 500° C. to 800°C., more preferably from 650° C. to 750° C., for a period of time in arange of from 0.5 to 5 minutes, preferably 1 to 3 minutes. During theheating the polyethylene glycol can be burned away, leaving a poroussilica film. Increasing the porosity of the silica reduces the index ofrefraction of the silica.

After heating, the film can be from 700 Å to 2000 μm (e.g., from 700 Åto 2000 Å, or from 700 Å to 1400 Å) thick.

The invention having been generally described, reference is now made tothe following examples, which are provided below for purposes ofillustration only and are not intended to limit the scope of theinvention as defined by the claims.

EXAMPLES

The following examples are intended to be illustrative of the method ofthe present invention. Other compounds to be used and methods will berecognized and appreciated by those of skill in the art.

Liquid compositions shown in Table 1 below were prepared by mixingtogether tetraethyl orthosilicate (TEOS), a solution of 30 gpolyethylene glycol (PEG) in 100 ml water, a solution of 37 weight % HClin water, n-butanol, and ethanol. The liquid compositions at roomtemperature were sprayed in air onto at least one surface of a glasssheet at room temperature, thereby forming a liquid film. The ethanoland n-butanol evaporated from the liquid film, thereby forming a solidfilm. The solid film was heated to 700° C. for 2 minutes to form asilica film. The anti-reflective coating efficiency, or lighttransmission of each silica/glass sheet structure compared with thelight transmission of an uncoated reference glass sheet, is alsoreported in Table 1.

TABLE 1 n- Time for Trans- buta- complete mission nol evaporation in-TEOS (vol PEG/ of liquid crease No. (vol %) PEG aqHCl %) TEOS (sec) (%)1 2 2 1 0 1 20 1 2 2 2 1 1 1 40 1.5 3 2 2 1 2 1 60 2 4 2 2 1 5 1 90 2.55 2 4 1 5 2 90 4 PEG = vol % of a solution of 30 g polyethylene glycol(Mw = 8000) in 100 ml water; aqHCl = vol % of a solution of 37 weight %HCl in water; The remainder of each liquid composition was ethanol;PEG/TEOS = ratio of the volume % of a solution of 30 g polyethyleneglycol in 100 ml water to the volume % of tetraethyl orthosilicate.

Table 1 shows that the increase in light transmission by coating asilica film on a glass sheet is mainly driven by PEG/TEOS (i.e., theratio of the volume % of a solution of 30 g polyethylene glycol in 100ml water to the volume % of tetraethyl orthosilicate). A maximumincrease in light transmission of 4% was achieved with a PEG/TEOS of 2.A PEG/TEOS of I achieved an increase in light transmission no greaterthan 2.5%.

Table 1 also shows that for a constant PEG/TEOS ration of 1, addingn-butanol to the liquid compositions slowed the evaporation rate of theethanol and n-butanol liquid from the liquid films and increased thelight transmission of the silica/glass sheet structures formed byheating the solid films that remained after the liquid evaporation. Whenthe liquid evaporated in 20, 40, 60 and 90 seconds, the lighttransmission increase was 1%, 1.5%, 2% and 2.5%, respectively. Thisshows decreasing the liquid evaporation rate by adding n-butanolresulted in an increase in light transmission.

The anti-reflective films described in the Examples were made from thegeneral method comprising preparing a liquid composition comprising 0.1to 5 volume % of tetraethyl orthosilicate, 0.231 to 11.5 g ofpolyethylene glycol per liter of the liquid composition, 0.444 to 8.88 gof HCl per liter of the liquid composition, 0.1 to 20 volume % ofn-butanol, and a balance of ethanol; applying the liquid compositiononto a surface of a substrate to form a liquid film; evaporating thealcohols from the liquid film to form a solid film; and heating thesolid film to form a silica film.

In the Examples, the polyethylene glycol had a weight average molecularweight (Mw) in the range of from 4000 to 16000. Assuming that the 30 gpolyethylene glycol in 100 ml water has a density of 1 g/ml, the “0.1 to5 volume % of a solution of 30 g polyethylene glycol in 100 ml” water isapproximately equal to the 0.231 to 11.5 g of polyethylene glycol perliter of the liquid composition.

Assuming that the solution of 37 weight % HCl in water has a density of1.2 g/ml, the 0.1 to 2 volume % of a solution of 37 weight % HCl inwater is approximately equal to the 0.444 to 8.88 g of HCl per liter ofthe liquid composition. The solution of 37 weight % HCl in water iscommercially available hydrochloric acid known as reagent grade.

During the mixing, the ratio (PEG/TEOS) of the volume % of the solutionof 30 g polyethylene glycol in 100 ml water to the volume % oftetraethyl orthosilicate can be in a range of from 0.02 to 50. Toimprove the anti-reflective coating efficiency, the ration of PEG/TEOSis preferably at least 1; more preferably at least 2.

The starting composition in the Examples generally contained 1 to 3volume % of tetraethyl orthosilicate, 4.6 to 6.9 g of polyethyleneglycol per liter of the liquid composition, 1.78 to 2.66 g of HCl perliter of the liquid composition and 1 to 15 volume % of n-butanol.

While the present invention has been described with respect to specificembodiments, it is not confined to the specific details set forth, butincludes various changes and modifications that may suggest themselvesto those skilled in the art, all falling within the scope of theinvention as defined by the following claims.

1. A method of preparing a coating comprising Si on a substrate, themethod comprising: (i) preparing a composition comprising a compoundcomprising Si and O, a polymeric glycol, a strong acid, at least a firstalcohol, at least a second alcohol and water; (ii) applying thecomposition onto a surface of a substrate to form a film; (iii)evaporating the alcohols from the film; and (iv) heating the film;wherein at least one alcohol has a higher boiling point than at leastthe other alcohol and is miscible with at least the other alcohol andwater.
 2. The method according to claim 1, wherein preparing thecomposition comprises mixing together to form a liquid composition: 0.1to 15 volume % of a compound comprising Si and O; 0.1 to 80 g of apolymeric glycol per liter of composition; 0.1 to 20 g of strong acidper liter of composition; 0.1 to 80 volume % of at least one alcoholhaving a higher boiling point than at least one other alcohol containedin the composition; and a balance of the other alcohol contained in thecomposition.
 3. The method according to claim 1, wherein preparing thecomposition comprises mixing together to form a liquid composition: 0.1to 10 volume % of a compound comprising Si and O; 0.1 to 15 g of apolymeric glycol per liter of composition; 0.1 to 15 g of strong acidper liter of composition; 0.1 to 20 volume % of at least one alcoholhaving a higher boiling point than at least one other alcohol containedin the composition; and a balance of the other alcohol contained in thecomposition.
 4. The method according to claim 1, wherein preparing thecomposition comprises mixing together to form a liquid composition: 0.1to 5 volume % of a compound comprising Si and O; 0.1 to 10 g of apolymeric glycol per liter of composition; 0.1 to 10 g of strong acidper liter of composition; 0.1 to 20 volume % of at least one alcoholhaving a higher boiling point than at least one other alcohol containedin the composition; and a balance of the other alcohol contained in thecomposition.
 5. The method according to claim 2, wherein during themixing, a ratio of a volume % of the polymeric glycol per liter ofcomposition to the volume % of the compound comprising Si and O is atleast
 1. 6. The method according to claim 1, wherein the compoundcomprising Si and O is selected from the group consisting of silanes,silicates, siloxanes and silanols.
 7. The method according to claim 1,wherein the compound comprising Si and O is tetraethyl orthosilicate. 8.The method according to claim 1, wherein the polymeric glycol isselected from the group consisting of polyalkyl glycols and polyalkyleneglycols.
 9. The method according to claim 1, wherein the polymericglycol is polyethylene glycol.
 10. The method according to claim 1,wherein the strong acid is selected from the group consisting of nitricacid, hydrochloric acid, sulfuric acid and hydrobromic acid.
 11. Themethod according to claim 1, wherein the strong acid is hydrochloricacid.
 12. The method according to claim 1, wherein the strong acid isnitric acid.
 13. The method according to claim 1, wherein at least thefirst alcohol is ethanol.
 14. The method according to claim 1, whereinthe first alcohol is ethanol, and the second alcohol has a boiling pointthat is higher than the boiling point of ethanol.
 15. The methodaccording to claim 1, wherein the first alcohol is ethanol, and thesecond alcohol is selected from the group consisting of propanol,butanol and pentanol.
 16. The method according to claim 1, wherein thefirst alcohol is ethanol, and the second alcohol is n-butanol.
 17. Themethod according to claim 1, wherein applying the composition comprisesdipping, brushing, spinning or spraying the composition onto the surfaceof the substrate.
 18. The method according to claim 1, wherein applyingthe composition comprises spraying the composition onto the substrate.19. The method according to claim 1, wherein the substrate is selectedfrom plastic or glass.
 20. The method according to claim 19, wherein thesubstrate is photovoltaic glass having at least one smooth or patternedsurface.
 21. The method according to claim 1, wherein, during theapplying, the substrate is at room temperature and atmospheric pressure.22. The method according to claim 1, wherein, during the applying, theliquid composition is at room temperature.
 23. The method according toclaim 1, wherein, during the applying, the substrate is at a temperatureof 50° C. or above.
 24. The method according to claim 1, wherein, duringthe applying, the liquid composition is at a temperature of 50° C. orabove.
 25. The method according to claim 1, wherein the evaporation ofthe alcohols takes 60 seconds or more.
 26. The method according to claim1, wherein the heating is at a temperature in a range of from 500° C. to800° C.
 27. The method according to claim 1, wherein after heating, thefilm is between 700 and 1400 Å thick.
 28. The method according to claim1, wherein after heating, the film is porous.
 29. A method of increasingthe transmission of light through a substrate, the method comprising:(i) preparing a composition comprising a compound comprising Si and O, apolymeric glycol, a strong acid, at least two alcohols and water; (ii)applying the composition onto a surface of a substrate to form a film onthe substrate; (iii) evaporating the alcohols from the film; and (iv)heating the film; wherein at least one alcohol has a higher boilingpoint than the other and is miscible with both the other alcohol andwater; and wherein, after heating, the transmission of light through thesubstrate comprising said film is increased by at least 0.5% whencompared to the transmission of light through the substrate notcomprising said film.
 30. A method of making a coating comprising Si ona substrate, the method comprising: (i) preparing a compositioncomprising tetraethyl orthosilicate, polyethylene glycol, HCl, ethanol,at least one alcohol having a higher boiling point than ethanol, andwater; (ii) applying the composition onto a surface of a substrate toform a film; (iii) evaporating the at least one alcohol and the ethanolfrom the film; and (iv) heating the film; wherein the at least onealcohol having a higher boiling point than ethanol is miscible with bothethanol and water.
 31. The method according to claim 30, whereinpreparing the composition comprises mixing together to form a liquidcomposition: 0.1 to 10 volume % of tetraethyl orthosilicate, 0.1 to 20volume % of a solution of 30 g polyethylene glycol in 100 ml water, 0.1to 2 volume % of a solution of 37 weight % HCl in water, 0.1 to 80volume % of at least one alcohol having a higher boiling point thanethanol, and a balance of ethanol.
 32. The method according to claim 31,wherein during the mixing, a ratio of the volume % of the solution of 30g polyethylene glycol in 100 ml water to the volume % of tetraethylorthosilicate is at least 0.5.
 33. The method according to claim 30,wherein the at least one alcohol comprises a monohydric alcohol.
 34. Themethod according to claim 30, wherein the at least one alcohol comprisesn-butanol.
 35. The method according to claim 30, wherein the compositioncomprises 1 to 3 volume % of tetraethyl orthosilicate.
 36. The methodaccording to claim 30, wherein the composition comprises 4.6 to 6.9 g ofpolyethylene glycol per liter of the composition.
 37. The methodaccording to claim 30, wherein the composition comprises 1.78 to 2.66 gof HCl per liter of the composition.
 38. The method according to claim30, wherein the composition comprises 1 to 20 volume % of the at leastone alcohol having a higher boiling point than ethanol.
 39. The methodaccording to claim 30, wherein the substrate is selected from the groupconsisting of plastic and glass.
 40. The method according to claim 30,wherein the substrate is photovoltaic glass having at least one smoothor patterned surface.
 41. The method according to claim 30, wherein,during the applying, the substrate is at room temperature andatmospheric pressure.
 42. The method according to claim 30, wherein,during the applying, the liquid composition is at room temperature. 43.The method according to claim 30, wherein, during the applying, thesubstrate is at a temperature of 50° C. or above.
 44. The methodaccording to claim 30, wherein, during the applying, the liquidcomposition is at a temperature of 50° C. or above.
 45. The methodaccording to claim 30, wherein the applying comprises spraying thecomposition onto the surface of the substrate.
 46. The method accordingto claim 30, wherein the evaporation of the at least one alcohol and theethanol takes 60 seconds or more.
 47. The method according to claim 30,wherein the heating is at a temperature in a range of from 500° C. to800° C.
 48. The method according to claim 30, wherein after heating, thefilm is between 700 Å and 2000 μm thick.
 49. The method according toclaim 30, wherein after heating, the film is porous.
 50. A method ofmaking an anti-reflective coating, the method comprising preparing aliquid composition comprising 0.1 to 5 volume % of tetraethylorthosilicate, 0.231 to 20 g of polyethylene glycol per liter of theliquid composition, 0.444 to 8.88 g of HCl per liter of the liquidcomposition, 0.1 to 20 volume % of at least one alcohol having a higherboiling point than ethanol and miscibility with both ethanol and water,and a balance of ethanol; applying the liquid composition onto a surfaceof a substrate to form a liquid film; evaporating the at least onealcohol and the ethanol from the liquid film to form a solid film; andheating the solid film to form a silica film.
 51. The method accordingto claim 50, wherein the liquid composition is prepared by mixingtogether 0.1 to 5 volume % of tetraethyl orthosilicate, 0.1 to 5 volume% of a solution of 30 g polyethylene glycol in 100 ml water, 0.1 to 2volume % of a solution of 37 weight % HCl in water, 0.1 to 20 volume %of at least one alcohol having a higher boiling point than ethanol andmiscibility with both ethanol and water, and a balance of ethanol. 52.The method according to claim 51, wherein during the mixing a ratio ofthe volume % of the solution of 30 g polyethylene glycol in 100 ml waterto the volume % of tetraethyl orthosilicate is at least 0.5.
 53. Themethod according to claim 50, wherein the at least one alcohol comprisesa monohydric alcohol.
 54. The method according to claim 50, wherein theat least one alcohol comprises n-butanol.
 55. The method according toclaim 50, wherein the liquid composition comprises 1 to 3 volume % oftetraethyl orthosilicate.
 56. The method according to claim 50, whereinthe liquid composition comprises 4.6 to 6.9 g of polyethylene glycol perliter of the liquid composition.
 57. The method according to claim 50,wherein the liquid composition comprises 1.78 to 2.66 g of HCl per literof the liquid composition.
 58. The method according to claim 50, whereinthe liquid composition comprises 1 to 20 volume % of the at least onealcohol having a higher boiling point than ethanol and miscibility withboth ethanol and water.
 59. The method according to claim 50, whereinthe substrate is selected from the group consisting of plastic andglass.
 60. The method according to claim 50, wherein the substrate isphotovoltaic glass having at least one smooth or patterned surface. 61.The method according to claim 50, wherein during the applying thesubstrate is at room temperature and atmospheric pressure.
 62. Themethod according to claim 50, wherein during the applying the liquidcomposition is at room temperature.
 63. The method according to claim50, wherein during the applying the substrate is at a temperature of 50°C. or above.
 64. The method according to claim 50, wherein during theapplying the liquid composition is at a temperature of 50° C. or above.65. The method according to claim 50, wherein the applying comprisesspraying the liquid composition onto the surface of the substrate. 66.The method according to claim 50, wherein the evaporation of the atleast one alcohol and the ethanol from the liquid film to form the solidfilm takes 60 seconds or more.
 67. The method according to claim 50,wherein the heating is at a temperature in a range of from 500° C. to800° C.
 68. The method according to claim 50, wherein the silica film isbetween 700 Å and 2000 μm thick.
 69. The method according to claim 50,wherein the silica film is porous.
 70. A coating on a substrate made bythe method of claim
 1. 71. A coating on a substrate made by the methodof claim
 29. 72. A coating on a substrate made by the method of claim30.
 73. A coating on a substrate made by the method of claim 50.